Sulfonato-organosilanol compounds and aqueous solutions

ABSTRACT

Sulfonato-organosilanol compounds and aqueous solutions and compositions thereof are provided which have at least one sulfonato-organic substituent therein. The weight percentage of oxygen in the compounds is at least about 30% and the weight percentage of silicon in the compounds is not greater than about 15%, these percentages being taken with reference to the water-free acid form of the compounds. Hydrophilic siliceous surfaces and processes for imparting hydrophilicity to such surfaces are also provided.

BACKGROUND OF THE INVENTION

This invention relates to materials useful in the treatment of siliceoussurfaces. More particularly it relates to compounds, aqueous solutionsand compositions which are useful in imparting durable hydrophilicity tosiliceous surfaces.

Although various types of materials have been suggested for use inimparting hydrophilicity to various substrates, all of such previouslysuggested materials have been less than desirable for one reason oranother. For example, some of the earliest suggested materials for suchuse were common anionic or non-ionic surfactants (e.g.,triethanolammonium oleate, sodium lauryl sulfate, sodiumdodecylbenzenesulfonate, polyoxyalkylene sorbitol). These surfactantshave been described for use in either solid or aqueous solution form.However, the major disadvantage associated with the use of such commonsurfactants is that the hydrophilicity and antifogging propertiesimparted by such materials simply do not exhibit very good durabilityduring use, (i.e., such materials are easily dissolved by water andremoved from the surface). Consequently, in order for such materials tobe effective they must be reapplied to the surface at frequentintervals.

Another type of surfactant which has been described for use in impartinghydrophilic properties is a terpolymer of dimethyl, silicone,polyethylene oxide, and polypropylene oxide. This type of surfactant,which is described, for example, in U.S. Pat. No. 3,337,351, suffersfrom the same drawbacks as discussed above, namely easy dissolution bywater.

Still another type of surface active agent is described in U.S. Pat. No.3,187,033. This type of material contains S-C bonded sulfo groups anddisplays physical and chemical properties similar to soaps. Thus, forexample, these materials exhibit substantial surface tension loweringcapabilities.

U.S. Pat. No. 3,507,897 describes siloxane surface active agents inaqueous media. These solutions preferably have a pH of from 5 to 8 sothat the agents do not degrade. Additionally, these agents are said toexhibit excellent surface tension lowering capabilities.

U.S. Pat. No. 3,328,449 describes sulfopropylated, organofunctionalsilane and siloxane materials which are useful as detergents, ionexchange resins, wetting agents, anti-stat agents and polymerizationcatalysts for siloxanes. It is said that these materials may be providedin solution form and that suitable solvents include water. However, itis also said that such solvents must not react with the solute. There isno discussion therein of stable aqueous solutions ofsulfonato-organosilanols or of siliceous surfaces rendered hydrophilicby treatment therewith.

U.S. Pat. No. 3,455,877 describes organosilicon epoxides wherein theepoxy group (or the radical containing the epoxy group) is attached tosilicon by a Si-C linkage. These materials are said to be useful asemulsifiers, plasticizers, lubricants, etc. They are also said to beuseful in preparing hydroxy sodium sulfonates by reacting the epoxideswith sodium sulfite. There is no discussion of the preparation of stableaqueous solutions of such compounds or of the durably hydrophilicsurfaces produced by contacting such compositions with siliceoussurfaces.

The present invention provides compounds, aqueous solutions andcompositions which are useful for imparting durable hydrophilicity tosiliceous surfaces as well as the durably hydrophilic surfacesthemselves. The hydrophilic treatments of the present invention areparticularly useful where easy grease and wax removal is desired orrequired. Thus, for example, the treatments are useful on glass surfacessuch as household windows, automobile windshields and windows,eyeglasses, and bathroom mirrors; glazed ceramic surfaces such asceramic tile and ceramic bathroom fixtures; and silicon oxide treatedpolymeric and non-polymeric surfaces.

Siliceous surfaces treated in accordance with the present invention arenot rendered grease or wax repellent (i.e., they are not madeoleophobic). Consequently, greases and waxes may attach to the treatedsurfaces. However, the treated surfaces are rendered readily cleanableso that grease and wax may be removed therefrom by simple water rinsingalone although very light rubbing may also be helpful in some instances.

Because the present invention imparts durable hydrophilicity tosiliceous surfaces, such surfaces may be readily cleaned even afterhaving been repeatedly previously soiled or marked by grease or wax andthen cleaned. Moreover, surfaces treated in accordance with the presentinvention are substantially easier to clean than are surfaces which havenot been so treated.

Examples of greases and waxes which have been found to be readilyremovable from surfaces treated in accordance with the present inventionare butter, margarine, lard, natural sebum (skin oil), artificial sebum,motor oils, motor greases, paraffin wax and wax pencil marks. Stillother substances such as elastomeric-based adhesives, pressure-sensitiveadhesives, thermoplastic (solvent soluble) adhesives, thermosettingadhesives, epoxy adhesives, silicon based adhesives, etc. are readilyremoved from these surfaces.

Preferably the sulfonato-organosilanol compounds are provided in aqueoussolutions. Surprisingly, such solutions are stable over long periods oftime even at relatively high concentrations of thesulfonato-organosilanol compounds (e.g., 10% to 15% by weight). Thus,the treatment activity of the solutions is retained and no precipitateis formed therein upon prolonged storage. Moreover, such solutions maybe provided at various concentrations of the sulfonato-organosilanolcompounds. Consequently, the solutions may be provided in a concentratedform for storage or shipping that may be later diluted for use.

Additionally the preferred aqueous solutions provide thin, durableantifogging coatings on siliceous surfaces. Thus individual waterdroplets will not form and remain on surfaces treated with saidsolutions (i.e., said surfaces do not fog over) despite repeatedexposures to conditions of high humidity.

Surprisingly the foregoing results are achieved even though thesulfonato-organosilanol compounds do not exhibit typical surfactantcharacteristics. Thus these compounds do not significantly affect thesurface tension of aqueous media.

SUMMARY OF THE INVENTION

In accordance with the present invention there are provided novelsulfonato-organosilicon compounds (sometimes referred to hereinafter assulfonato-silanols) having at least one sulfonato-organic substituent,wherein the weight percentage of oxygen in the compound is at leastabout 30%, and wherein the weight percentage of silicon in the compoundis not greater than about 15%, said percentages being taken withreference to the water-free acid form of the compound. As it is usedherein, the acid form of the silanol compound refers to a compound whichhas a sulfonato substituent of the formula --SO₃ ⁻ H⁺. All percentagedeterminations with respect to oxygen and silicon are calculatedrelative to this form whether or not the compound under discussion isitself the acid form or is present in an aqueous solvent and/or as asalt of the acid.

Two types of novel sulfonato-silanols are provided. They are theorganosilanol-sulfonic acids and the organosilanolate-sulfonic acidsalts (each of which are described more fully hereinafter).

Also provided herein are novel aqueous solutions and compositions of thesulfonato-organosilanol compounds. These aqueous solutions includesolutions of the novel organosilanol-sulfonic acids andorganosilanolate-sulfonic acid salts in addition to solutions of theknown organosilanol-sulfonic acid salts. As it is used herein, the term"aqueous solutions and compositions" refers to solutions andcompositions wherein water is present. Such solutions and compositionsmay employ water as the only solvent or they may employ combinations ofwater and organic solvents such as alcohol and acetone. Moreoversubstantial amounts of the organic solvents may be included in thecombinations.

Still further provided are articles comprising a siliceous surfacehaving a durably hydrophilic organic layer bound thereto. Also providedis a process for rendering siliceous surfaces durably hydrophilic.

DETAILED DESCRIPTION OF THE INVENTION

The sulfonato-organosilanol compounds of the invention may be preparedby converting the corresponding precursor organic silane to theorganosilanolate or the organosilanol-sulfonic acid salt followed bysubsequent conversion to the desired product.

Precursor silane materials which are useful in preparing the compoundsand solutions of the present invention have a reactive functional groupon the organic group and from one to three hydrolyzable groups on thesilicon atom. An example of one useful type of precursor silane is onebearing an epoxide group on the organic group. This material may beconverted to the organosilanolate-sulfonic acid salt by reacting analcohol or water solution thereof with an aqueous solution of an alkalisulfite. The silanolate salt may be converted to theorganosilanol-sulfonic acid by passing the silanolate solution throughan acidic ion exchange resin such as "Amberlite IR-120" (acid form)available from Rohm and Haas Company. Both the silanolate salt and thesulfonic acid may be converted to the neutral pH organosilanol-sulfonicacid salt by neutralizing them with, for example, by neutralizing withthe acid form.

An example of another type of useful precursor silane is one havingethylenic unsaturation in the organic group. This type of material maybe converted to the organosilanol-sulfonic acid salt by reacting analcohol solution thereof with an aqueous solution of an alkalibisulfite. The resultant sulfonic acid salt may be converted to thecorresponding organosilanol-sulfonic acid by passing thesilanol-sulfonic acid salt solution through an acidic ion exchangeresin. Alternatively, the organosilanol-sulfonic acid salt may beconverted to the organosilanolate-sulfonic acid salt by treating theorganosilanol-sulfonic acid salt solution with an appropriate base.

Yet another example of a useful type of precursor silane is one bearinga thiol (i.e., mercapto) group on the organic group. This material maybe converted to the corresponding organosilanol-sulfonic acid salt byoxidizing a solution of the precursor silane in acetone with an aqueoussolution of potassium permanganate. The resultant silanol-sulfonic acidsalt may then be converted to the corresponding organosilanol-sulfonicacid by passing the salt solution through an acidic ion exchange resin.Alternatively, the silanol-sulfonic acid salt may be converted to thecorresponding organosilanolate-sulfonic acid salt by reacting it with anappropriate base.

The sulfonato-organosilanol compounds used in the solutions andcompositions of the present invention have the formula ##STR1## whereinQ is selected from hydroxyl, alkyl groups containing from 1 to about 4carbon atoms and alkoxy groups containing from 1 to about 4 carbonatoms;

M is selected from hydrogen, alkali metals and organic cations of strongorganic bases having an average molecular weight of less than about 150and a pK_(a) of greater than about 11;

X is an organic linking group;

Y is selected from hydrogen, alkaline earth metals, (e.g., magnesium,calcium, etc.) organic cations of protonated weak bases having anaverage molecular weight of less than about 200 and a pK_(a) of lessthan about 11 (e.g., 4-aminopyridine, 2-methoxyethylamine, benzylamine,2,4-dimethylimidazole, 3-[2-ethoxy(2-ethoxyethoxy)]propylamine), alkalimetals and organic cations of strong organic bases having an averagemolecular weight of less than about 150 and a pK_(a) of greater thanabout 11 (e.g., ⁺ N(CH₃)₄, ⁺ N(CH₂ CH₃)₄), provided that M is hydrogenwhen Y is selected from hydrogen, alkaline earth metals and organiccations of said protonated weak bases;

r is equal to the valence of Y; and

n is 1 or 2.

The weight percentage of oxygen in these compounds is at least about30%, and preferably at least about 40%. Most preferably it is in therange of about 45% to 55%. The weight percentage of silicon in thesecompounds is no greater than about 15%. Each of these percentages isbased on the weight of the compound in the water-free acid form.

The organic linking group X, is preferably selected from alkylenegroups, cycloalkylene groups, alkyl-substituted cycloalkylene groups,hydroxy-substituted alkylene groups, hydroxy-substituted mono-oxaalkylene groups, divalent hydrocarbon groups having mono-oxa backbonesubstitution, divalent hydrocarbon groups having mono-thia backbonesubstitution, divalent hydrocarbon groups having monooxo-thia backbonesubstitution, divalent hydrocarbon groups having dioxo-thia backbonesubstitution, arylene groups, arylalkylene groups, alkylarylene groupsand substituted alkylarylene groups. Most preferably X is selected fromalkylene groups, hydroxy-substituted alkylene groups andhydroxy-substituted mono-oxa alkylene groups.

The organosilanol-sulfonic acids represent one class of novel compoundswithin the purview of formula I. These compounds have the formula##STR2## wherein Q, X and n are each as described above. Examples oforganosilanol-sulfonic acids of formula II are

    (HO).sub.3 --Si--X--CH.sub.2 SO.sub.3.sup.- H.sup.+        (IIA) ##STR3## In these formulae X is as described above and Q' is an alkyl group which contains from 1 to about 4 carbon atoms. Representative compounds of formulae IIA, IIB and IIC include: ##STR4## Of these specific compounds, those of formulae (a), (c), (d) and (i) are preferred. Compound (d) is a particularly preferred compound.

Useful starting materials in the preparation of compounds (a) through(i) above are respectively as follows:

    ______________________________________                                         ##STR5##                     (a')                                             ##STR6##                     (b')                                            (CH.sub.3 CH.sub.2 O).sub.3 SiCHCH.sub.2 or alternatively                                                   (c')                                            (CH.sub.3 CH.sub.2 O).sub.3SiCH.sub.2 CH.sub.2 SH                             (R'O).sub.3 SiCH.sub.2 CH.sub.2 CH.sub.2 SH or alternatively                                                (d')                                            (R'O).sub.3 SiCH.sub.2 CHCH.sub.2, where R' is methyl or ethyl                 ##STR7##                     (e' )                                            ##STR8##                     (f')                                            (R'O).sub.3SiCH.sub.2 CH.sub.2 CH.sub.2SCH.sub.2 CHCH.sub.2, or               alternatively                 (g')                                             ##STR9##                                                                      ##STR10##                    (h')                                             ##STR11##                    (i')                                            ______________________________________                                    

The aqueous solutions of the organosilanol-sulfonic acids are acidic.Thus they have a pH of less than about 5. Preferably they have a pH ofless than about 3. Most preferably they have a pH in the range of about0.5-2.5.

The organosilanolate-sulfonic acid salts represent another class ofnovel compounds within the purview of formula I. These compounds havethe formula ##STR12## wherein Q, X, n and r are each as defined above,and wherein Z is selected from alkali metals and organic cations ofstrong organic bases having an average molecular weight of less thanabout 150 and a pK_(a) of greater than about 11. Examples oforganosilanolate-sulfonic acid salts of formula III are ##STR13##Representative compounds of formulae IIIA and IIIB include: ##STR14##

The aqueous solutions of the organosilanolate-sulfonic acid salts arebasic. Thus they have a pH of greater than about 9. Preferably they havea pH of greater than about 10. Most preferably they have a pH in therange of about 11-13.

The known organosilanol-sulfonic acid salts represent yet another classof compounds within the purview of formula I which are useful in theaqueous solutions and compositions of the present invention. Thesecompounds have the formula ##STR15## wherein X, n and r are each asdescribed above, Q" is selected from hydroxyl and alkyl groupscontaining from 1 to about 4 carbon atoms and A is selected fromalkaline earth metals, organic cations or protonated weak bases havingan average molecular weight of less than about 200 and a pK_(a) of lessthan about 11, alkali metals and organic cations of strong organic baseshaving an average molecular weight of less than about 150 and a pK_(a)of greater than about 11. Examples of organosilanol-sulfonic acid saltsof formula IV are

    (HO).sub.3 --Si--XCH.sub.2 SO.sub.3.sup.- A.sup.+          (IVA)

    (HO).sub.2 --Si--(XCH.sub.2 SO.sub.3.sup.- A.sup.+).sub.2  (IVB)

Representative compounds of formula IVA and IVB include:

    (HO).sub.3 --Si--CH.sub.2 CH.sub.2 SO.sub.3.sup.- K.sup.+  (a)

    (HO).sub.2 --Si--(CH.sub.2 CH.sub.2 SO.sub.3.sup.- Na.sup.+).sub.2 (b)

The aqueous solutions of the organosilanol-sulfonic acid salts areneutral. Thus they have a pH in the range of about 5 to 9. Preferablythey have a pH in the range of about 6 to 8.

The aqueous solutions of the present invention may be used to imparthydrophilicity to a wide variety of substrates having siliceous surfaceswith closely adjacent SiOH sites. Examples of such surfaces includewindow glass, mirror glass, borosilicate glass, lead glass, fusedsilica, soda glass, glazed ceramics and ceramic tiles, ceramicelectrical insulations, decorative ceramics, porcelain ware, china ware,bone china, natural quartz, granite, feldspar, beryl, obsidian,enamelled iron and agate. Additionally polymeric and non-polymericsurfaces which have been vapor coated with a silicon oxide of theformula --SiO₂ -- where x is 1 to 2 often termed "silicon monoxide" maybe rendered hydrophilic in accordance with the present invention.Examples of polymeric surfaces which may be treated with silicon oxideand then rendered hydrophilic are polyester, polycarbonate,polyvinylchloride, polyvinylfluoride, polyvinylidene fluoride,polyimide, phenolic resin, polyethylene, nylon, polystyrene,polypropylene, cellulose acetate butyrate, polymethylmethacrylate, etc.Examples of non-polymeric surfaces which may be treated with saidsilicon oxide and then rendered hydrophilic are mica, aluminum, steel,painted surfaces, etc.

Preferably, the solutions used to treat the siliceous surfaces have aconcentration of the appropriate sulfonato-silanol compounds ofapproximately 1% to 3% by weight. Lower or higher concentrations of thesulfonato-silanols may also be used (e.g., 0.1% to 30% or higher) ifdesired.

Siliceous surfaces may be easily rendered durably hydrophilic inaccordance with the present invention. Thus, an aqueous solution of asulfonato-organosilanol compound is applied to said surface under mildconditions (e.g., 10° C. to 60° C. at atmospheric pressure) followed bysimple drying at room temperature (e.g., 23° C.) to obtain thehydrophilic properties. No catalyst or curative is needed in order toobtain these properties.

The hydrophilic treatment composition may be applied directly to thesiliceous surfaces, especially to the silicon oxide treated polymericand non-polymeric surfaces. However, it is preferred that the glass andglazed ceramic surfaces to be treated be freshly cleaned and activatedeither immediately prior to, or simultaneously with, the application ofthe aqueous solution. It has been found that the amount of thesulfonato-organosilanol compound which bonds to these substrates tendsto be reduced as the length of time between the cleaning-activation stepand the treatment step is increased. Moreover, such a delay also tendsto diminish the durability of the hydrophilic surface.

A variety of techniques may be employed to clean and activate thesurface. For example an abrasive household cleanser containing finesilica particles such as Ajax® or an abrasive polishing material such assilica, alumina, talc, quartz, cerium oxide, zirconium oxide etc. isutilized followed by rinsing and, usually, drying. The surface may alsobe cleaned and activated by contacting it with materials such ashydrofluoric acid, chromic sulfuric acid, sodium hydroxide solutions,etc. again followed by rinsing and usually drying.

The exact material used to clean and activate the surface is somewhatdependent upon the nature of the treatment solution employed. Thus it ispreferred that an abrasive material such as Ajax® be employed incleaning and activating the surface when an acidic or neutral pHtreatment solution is to be employed. When a basic treatment solution isto be employed it is preferred that an acidic material such ashydrofluoric acid be employed in cleaning and activating the surface.

Alternatively an abrasive or polishing material may be incorporated intothe aqueous solution so that the surface to be rendered hydrophilic maybe cleaned, activated and made hydrophilic in one step. In this case thesurface may be buffed with a soft dry cloth or rinsed with water toremove the abrasive material after application of the aqueous solutionand conditioning.

It is preferred that the treatment be dried for a period of time beforethe surface is soiled or rinsed. During this time thesulfonato-organosilanol compound interacts with the siliceous surfaceand forms a durable hydrophilic layer thereon. At this point the treatedsurface may be described as "conditioned". It is believed that theorganosilicon hydrophilic layer is formed when the ##STR16## portion ofthe sulfonato-silanol reacts with available Si--OH sites on thesiliceous surface to form Si--O--Si bonds thereon.

The treated surfaces are rendered effectively durably hydrophilic withina relatively short period of time after dryness has been obtained. Forexample, when aqueous solutions of the organosilanol-sulfonic acids areemployed the surface may be rendered durably hydrophilic after as littleas one minute of conditioning. However, typically about 15 minutes ofconditioning time is preferred. When an organosilanolatesulfonic acidsalt is employed the surface of the treated substrate is rendereddurably hydrophilic after about 24 hours of conditioning. However, thedegree of hydrophilicity tends to continue to improve over the first fewdays after treatment. When the organosilanol-sulfonic acid salt isemployed the treated surface is rendered durably hydrophilic after about2 hours of conditioning. The degree of hydrophilicity tends to continueto improve over the first few hours after treatment.

Although the compositions of the invention can be used to impart a highdegree of hydrophilicity to a surface, it is also possible to convertthe resulting hydrophilic surface to a hydrophobic surface by means ofion exchange. That is, the hydrophilic surface may be rinsed orotherwise contacted with certain cationic surfactants, quaternary fattyamines, etc., so that the sulfonato-organosilanol compound bonded to thesurface of the substrate is converted to a salt of an organic cationbearing a hydrophobic tail. The process is totally reversible andaccordingly, the surface may be converted back to a very hydrophilicstate again (e.g., by treatment with aqueous alkali salt solutions) asdesired.

The aqueous solutions of the present invention may be provided in theform of compositions having a variety of viscosities. Thus, for example,the viscosity may vary from a water thinness to a paste-like heaviness.They may also be provided in the form of gels. Additionally, a varietyof other ingredients may be incorporated in the aqueous solutions. Thus,for example, abrasive materials (or polishing agents), conventionalanionic surfactants and detergents and suspending aids or thickeningagents may be included therein.

The abrasive materials or polishing agents may have a variety ofparticle sizes. However, it is preferred that they not be so large as tovisibly abrade the surface which is treated. These materials maycomprise up to about 60% by weight of the composition. Preferably theycomprise from about 5% to 10% by weight of the composition. The exactabrasive material selected is dependent upon the acidity of the aqueoussolution. Thus acidic abrasive materials are employed when acidictreatment solutions (i.e., solutions of organosilanol-sulfonic acids)are employed. Basic abrasive materials are employed when basic treatmentsolutions (i.e., solutions of organosilanolate-sulfonic acid salts) areemployed. Acidic or basic abrasive materials may be employed whenneutral treatment solutions (i.e., a solutions of organosilanol-sulfonicacid salts) are employed. Representative examples of useful abrasivematerials or polishing agents include amorphous silica (e.g., "Imsil"A-10, A-15 and A-25, commercialy available from Illinois MineralCompany), calcium carbonate, talc, silicon carbide, α-quartz, alumina,zirconium oxide, cerium oxide, etc.

The anionic surfactants and detergents included in the aqueous solutionsand compositions of the invention typically comprise up to about 5% byweight of the composition. Preferably they comprise from about 0.1 to 1%by weight of the composition. More or less of the surfactants ordetergents may be utilized if desired. Representative examples of usefulsurfactants or detergents include sodium dodecylbenzenesulfonate("Siponate" DS-10 available from Alcolac Incorporated), sodiumdodecyldiphenyloxidedisulfonate ("Dowfac" 2Al available from DowChemical Company), sodium dodecyl sulfate, C₈ F₁₇ SO₃ H, sodiumdioctylsulfosuccinate, (Aerosol® OT, available from American CyanamidCompany), sodium heptadecyl sulfate (Tergitol® Anionic 7, commerciallyavailable from Union Carbide Corporation).

The suspending or thickening aids which may be employed in compositionsof the present invention must be compatible with the aqueous solutionsof the invention. Thus the thickening aids must maintain the abrasivematerial (described hereinbefore) in an easily redispersible state foran extended period of time (e.g., 12 months or more). Thus usefulthickening aids prevent the formation of a hard cake of abrasivematerial. Additionally the suspending or thickening aids are chemicallystable in the aqueous composition. That is they do not degrade thereinor adversely affect the performance of the composition.

The suspending or thickening aids typically comprise up to about 5% byweight of the composition. Preferably they comprise from about 0.1% to1% by weight of the composition. However, more or less of such aids maybe employed if desired. Representative examples of useful thickening orsuspending aids include magnesium aluminum silicates such as "Veegum"HV, K and T available from R. T. Vanderbilt Company, "Gel White" GT and"Mineral Colloid MO" available from Georgia Kaolin Company, and"Ben-A-Gel" available from National Lead Industries. Other usefulsuspending or thickening aids include fumed silica such as Cab-O-Sil®M-5 available from Cabot Corporation and xanthan gums such as "Keltrol"available from Kelco Corporation.

Solvents may also be included in the hydrophilic treatment solutions andcompositions so as to improve their freeze-thaw stability. Typically thesolvents comprise up to about 40% by weight of the compositions andpreferably in the range of about 5-10% by weight of the compositions.Representative examples of useful solvents include the lower alcoholssuch as methanol, ethanol, propanol, 2-propanol, etc. A variety of othersolvents might also be used as will be apparent from this specification.

The hydrophilic layer obtained by the treatment described hereinbeforeis transparent, haze-free, thin and durable. Thus, for example, acleaned and activated glass surface which has been treated with anaqueous solution of the present invention possesses optical qualitiescomparable to those of a non-treated but cleaned glass surface. That is,both the reflectance and transmission of the treated glass surface areessentially identical to those of the untreated glas surface.

Moreover, these hydrophilic layers are extremely thin, being less thanabut 100 nanometers thick. The thinness of the layers may be shown by avariety of techniques such as X-ray Photoelectron Spectroscopy (ESCA),Ion Scattering Spectroscopy (ISS), Secondary Ion Mass Spectrometery(SIMS), radiolabeled ³⁵ S and ellipsometry. These techniques indicatethat the hydrophilic layer is less than 100 nanometers thick and, oftencorresponds to a thinness calculated to be in the range of 1 to 2molecular layers of the sulfonato-organosilanol compound used in theaqueous treatment solution.

A variety of techniques may be employed to demonstrate the durability ofthe hydrophilic treatment. These techniques include the use ofradiolabelled ³⁵ S, a Cationic Dye Exchange test and a "Spreading WaterDrop" test. Typically these tests are employed in conjunction with a"Cyclic Wear" test. These techniques are now described in more detail.

RADIOLABELLED ³⁵ S TEST

Radioactive ³⁵ S in an alkali sulfite is used to prepare an aqueoussolution of the desired sulfonato-organosilanol compound. This solutionis applied to a freshly cleaned and activated siliceous surface andallowed to condition thereon. The treated surface is then rinsed withdeionized water to remove any non-bonded radiolabelledsulfonato-organosilanol compound. The radioactivity of the treatedsurface is then determined by means of a flow-counter gas ionizationsystem (available as Model 186 from Nuclear Chicago Corporation).

CATIONIC DYE EXCHANGE TEST

A section of a siliceous surface to be tested is contacted with anexcess of a 0.01 molar solution (pH of 4) of a cationic dye (U.S.P.methylene blue (chloride) dye) in deionized water. The dye solution isallowed to dry thereon and bind to the surface of the section. Thesection is then rinsed with deionized water to remove any unbound dye,the remaining bound dye is then removed from the surface by carefullyrinsing it with 3 ml of a 0.5% by weight solution of the potassium saltof perfluoro(ethylcyclohexane) sulfonic acid in absolute ethanol. Therinse solution is collected and the dye concentration therein determinedby measuring the spectrophotometric absorbance thereof in a 10 mm cellat a wavelength of 655 nanometers (nm). A high absorbance in the rinsesolution indicates that there is a high level of sulfanato-organosiliconcompound on the surface of the section. Direct densitometry may also beutilized to measure dye binding.

Siliceous substrates treated in accordance with the present inventionbind at least about 50% (and preferably at least about 100%) by weightmore of the methylene blue dye expressed as the chloride than do therespective normal siliceous surfaces. Normal siliceous surfaces arethose which are clean and equilibrated and free of hydrophilictreatments and other foreign matter. Normal surfaces may be prepared bya process of normalization wherein the surface has been cleaned andactivated and then allowed to equilibrate over a 24 hour period in anambient atmosphere at room temperature. The cleaning and activating mayinvolve abrasive polishing, treating with acidic or basic solutions, orflame (heat) treatment followed by rinsing with deionized water andcareful drying at ambient (e.g., 23° C.) temperature. For example,normalization may be achieved by (i) soaking the treated surface in achromic/sulfuric acid cleaning solution at about 23° C. for 16 hours,(ii) rinsing it with deionized water and (iii) air drying it at about23° C. for 24 hours. This latter treatment is especially suited forremoving existing hydrophilic organic layers to permit comparisionmeasurements of normalized siliceous substrates.

SPREADING WATER DROP TEST

A section of a siliceous surface to be tested is either cleaned andactivated with an aqueous slurry of an abrasive material or cleaned,activated and rendered hydrophilic according to the invention. Thehydrophilically treated surface is allowed to condition for the desiredtime. A one microliter (1.0 μl) drop of deionized water is placed on theappropriate horizontally oriented siliceous surface. The area covered bythe drop of water is then determined. An area of coverage of less thanabout 10 mm² is indicative of a nonhydrophiic surface while an area ofcoverage of more than about 10 mm² or more is indicative of ahydrophilic surface (i.e., one exhibiting grease and wax release). Asthe degree of hydrophilicity of the treated surface increases the areaof coverage also increases. Thus an area of 12 mm² or more is indicativeof a hydrophilic surface having easy grease and wax release while anarea of 15 mm² or more is indicative of a surface having goodanti-fogging characteristics.

CYCLIC WEAR TEST

A surface to be tested is placed in a Gardner Straight Line Washabilityand Abrasion Machine. A pad of wet cheesecloth under a pressure of about4 kilopascals is placed over the surface and passed back and forthrepeatedly thereover. Each cycle equals one back and forth pass of thecheesecloth pad.

The foregoing invention is further illustrated by means of the followingexamples:

EXAMPLE 1

An organosilanolate-sulfonic acid salt having the formula ##STR17## wasprepared. A solution comprising 0.5 gram (g)gammaglycidoxypropyltrimethoxy silane and 2.5 g methanol was addedslowly to a solution of 0.27 g sodium sulfite (Na₂ SO₃) and 5 g water.The reaction mixture was stirred at 50° C. for 16 hours and then dilutedwith water to 3% by weight solids. A small amount of a surfactant (0.5%by weight sodium dodecylbenzenesulfonate) was added to the dilutedreaction mixture and agitated therewith until uniform to provide a basichydrophilic treatment solution having a pH of 12.8.

EXAMPLE 2

An organosilanol-sulfonic acid having the formula ##STR18## wasprepared. An 8% by weight solution of the organosilanolate-sulfonic acidsalt of Example 1 in a methanol/water mixture (2/1 by volume) was passedthrough an excess of the acid form of Amberlite® IR-120 (an ion exchangeresin commercially available from Rohm and Haas Company). This providedan acid treatment solution having a pH of 1.6. The solution was dilutedto 2% solids by weight with deionized water and 0.5% by weight sodiumdodecylbenzenesulfonate was added thereto to provide the finalhydrophilic treatment solution.

EXAMPLE 3

An organosilanol-sulfonic acid having the formula (HO)₃ SiCH₂ CH₂ SO₃ ⁻H⁺ was prepared. A solution of 83.6 g triethoxyvinylsilane and 1440milliliters (ml) absolute ethanol was added slowly to a solution of 100g sodium bisulfite, 10 g sodium nitrate, 10 g sodium nitrite and 2200 mlof water. This reaction mixture was stirred at about 23° C. for threedays. The mixture was then passed through approximately 800 g Amberlite®IR-120 (acid form) ion exchange resin. The pH of the final solution wasobserved to be about 1. About 0.5% by weight dodecylbenzenesulfonic acidwas then added to the reaction mixture and dissolved therein to providean acidic hydrophilic treatment solution.

EXAMPLE 4

An organosilanol-sulfonic acid salt having the formula (HO)₃ SiCH₂ CH₂SO₃ ⁻ K⁺ was prepared. A solution comprising 0.51 g (2 mmol)2-mercaptoethyltriethoxysilane and 4 ml acetone was added with stirringover a five minute period to an ice-bath cooled solution of 1.26 g (8mmol) potassium permanganate and 8 ml distilled water. The ice-bath wasremoved and stirring was continued for two hours. About 0.3% by weightsodium dodecylbenzenesulfonate was then dissolved in the reactionmixture. The mixture was then filtered to give a pale yellow neutralhydrophilic treatment solution which had a pH of about 8.

A portion of the solution was evaporated to recover the salt. Thestructure of the salt was confirmed by nuclear magnetic resonancespectra (nmr).

EXAMPLE 5

An organosilanol-sulfonic acid having the formula (HO)₃ SiCH₂ CH₂ CH₂SO₃ ⁻ H⁺ was prepared. A solution of 1.96 g (0.01 moles)gamma-mercaptopropyltrimethoxysilane and 20 ml acetone was added rapidlyto a solution of 3.16 g (0.02 moles) potassium permanganate and 60 ml ofwater. The resulting mixture turned brown and immediately warmed andincreased in pH to approximately 9. The mixture was filtered and theprecipitated MnO₂ washed with deionized water (300 ml). Approximately 2g of dried MnO₂ was recovered. The filtrate was ion exchanged asdescribed in Example 2 to provide an acidic hydrophilic treatmentsolution.

A portion of the product was recovered and titrated to determine theyield of sulfonic acid therein. The yield was calculated to be 86.8% onthe basis of the titration.

Alternative procedures for preparing the organosilanol-sulfonic acid ofthis example are possible. Thus the acid was also made by adding asolution of 4.4 g (22.4 mmol) gamma-mercaptopropyltrimethoxysilane and45 ml of reagent acetone to an ice-bath cooled solution of 17.8 g (113mmol) potassium permanganate and 90 ml distilled water with stirringover a five minute period. After the addition was complete the ice-bathwas replaced by a cold water bath and stirring was continued at 23° C.until all the permanganate had been consumed (about two hours). Theneutral pH mixture was filtered and ion-exchanged with Amberlite® IR-120(acid form) ion exchange resin to give an acidic treatment solution. Thestructure of the acid was confirmed by nmr. A small amount of asurfactant (i.e., 0.1-0.5% by weight sodium dodecylbenzenesulfonate) maybe added to the solution.

The organosilanol-sulfonic acid of this example was also prepared byslowly adding a solution of 2.04 g (10 mmol) allyltriethoxysilane and 35ml absolute ethanol to a stirred solution of 2.08 g (20 mmol) sodiumbisulfite, 0.2 g (2.9 mmol) sodium nitrite, 0.2 g (2.35 mmol) sodiumnitrate and 50 ml of distilled water. Stirring was continued at roomtemperature for 96 hours. The resulting product was rendered acidic byion exchange as described in Example 2. Analysis by nmr confirmed thestructure.

EXAMPLE 6

An organosilanol-sulfonic acid having the formula (HO)₃ SiCH₂ CH₂ CH₂SCH₂ CH₂ CH₂ SO₃ ⁻ H⁺ was prepared. Solid (CH₃ O)₃ SiCH₂ CH₂ CH₂ SCH₂CH₂ CH₂ SO₃ Na was prepared according to Example 1 of U.S. Patent No.3,508,959. This compound was reacted with and dissolved in water. Theresulting product was ion exchanged as described in Example 2 to give anacidic treatment solution.

EXAMPLE 7

An organosilanol-sulfonic acid having the formula (HO)₂ Si(CH₂ CH₂ SO₃ ⁻H⁺)₂ was prepared. A solution comprising 8.6 g (0.05 mol)divinyldiethoxysilane and 200 ml absolute ethanol was slowly addeddropwise to a stirred solution comprising 15.6 g (0.15 mol) sodiumbisulfite, 1.56 g (18.4 mmol) sodium nitrate, 1.56 g (22.6 mmol) sodiumnitrite and 300 ml distilled water. Stirring was continued at roomtemperature for 72 hours after which the solution was ion exchanged asdescribed in Example 2 to give an acidic hydrophilic treatment solution.About 0.5% by weight sodium dodecylbenzene-sulfonate was added to thesolution.

Prior to ion exchange, a portion of the sodium salt solution wasexamined using nmr and infrared (IR) analysis. Both confirmed thestructure of the salt.

EXAMPLE 8

An organosilanol-sulfonic acid having the formula ##STR19## wasprepared. A solution of 2.6 g (20 mmol) dimethylvinyl ethoxysilane and66 ml absolute ethanol was added dropwise to a stirred solution of 4.54g (43.6 mmol) sodium bisulfite, 0.45 g (5.3 mmol) sodium nitrate, 0.45 g(6.5 mmol) sodium nitrite and 100 ml of distilled water. Stirring wascontinued at room temperature for 96 hours to form the sodium salt ofthe sulfonic acid. The solution of the salt was ion exchanged asdescribed in Example 2 to give an acid hydrophilic treatment solution.About 0.5% by weight sodium dodecylbenzenesulfonate was dissolved in thesolution.

Prior to ion exchange, a portion of the solution was examined by nmr andIR techniques. These tests confirmed the above salt structure. Thecalculations also showed that the water-free acid form of theorganosilanol-sulfonic acid was 15.2% silicon and 34.7% oxygen byweight.

EXAMPLE 9

An organosilanol-sulfonic acid having the formula ##STR20## wasprepared. A solution of 2.5 g (10 mmol)p-chloromethylphenyltrimethoxysilane and 25 ml absolute ethanol wasslowly added dropwise to a stirred solution of 1.26 g (10 mmol) sodiumsulfite and 30 ml distilled water. The mixture was stirred in a 75° C.oil bath for two hours and then at room temperature overnight to producethe sodium salt. The solution was then ion exchanged as described inExample 2 to give an acidic treatment solution. About 0.5% by weightsodium dodecylbenzenesulfonate was dissolved in the solution. Thestructure of the acid form was confirmed by nmr and IR techniques.

EXAMPLES 10-21

Thin coatings of the treatment solutions of Examples 1-9 were applied toseparate glass and glazed ceramic substrates. In each case thesubstrates were cleaned and activated by scouring with a slurry of waterand an abrasive household cleanser (e.g., Ajax®) followed by waterrinsing and drying with a soft dry cloth before application of thetreatment solution. A clean cellulosic pad (e.g., a Colitho® plate wipe)was used to immediately apply the treatment solutions as a thin visiblydamp film. The resulting coatings were conditioned at room temperatureand then tested for hydrophilicity by determining the ease with whichsubstances such as butter, sebum (skin oil), artificial sebum, waxpencil marks and paraffin wax were removed from the treated surfaces.The treatment compositions and the conditioning times employed are setforth in Table 1. In each example both a glass and a glazed ceraicsurface was tested.

                  TABLE 1                                                         ______________________________________                                                  TREATMENT      CONDITIONING                                         EXAMPLE   COMPOSITION    TIME                                                 ______________________________________                                        10        Ex. 1          3 Days                                               11        Ex. 2          3 Hours                                              12        Ex. 2          15 Min.                                              13        Ex. 3          3 Min.                                               14        Ex. 4          2 Hours                                              15        Ex. 5          5 Min.                                                         (1st Process)                                                       16        Ex. 6          3 Hours                                              17        Ex. 7          2 Min.                                               18        Ex. 8          1 Hour                                               19        Ex. 8          2 Hour                                               20        Ex. 8          15 Min.                                              21        Ex. 9          2 Hour                                               ______________________________________                                    

Each of the compositions provided durable hydrophilic treatments on boththe glass and glazed ceramic surfaces. Moreover, each of the treatmentsallowed easy removal of the above-described substances by simply rinsingthe treated surface with cold water. However, the substances were notremoved from the untreated glass or glazed ceramic surfaces by simplerinsing with cold water.

EXAMPLE 22

The durable hydrophilicity of glass and glazed ceramic surfaces treatedaccording to the invention was demonstrated. The glass and glazedceramic surfaces were cleaned and activated as described in Examples10-21 and then immediately made hydrophilic by applying a thin layer ofthe organosilanolatesulfonic acid salt treatment solution of Example 1thereto with a Colitho® plate wipe. The treated surfaces wereconditioned for three days. When the Spreading Water Drop test wasperformed on the treated glass surface the drop covered an area of about18 mm². When the Spreading Water Drop test was performed on an untreatedglass surface the drop covered an area of only about 8 mm².

The treated surfaces were then tested for durability by marking themwith a wax pencil (Reliance® All-Surface Writer, White No. 3366);rinsing the surface with water from a wash bottle; and drying thesurface with a soft dry towel. The cycle was repeated for a total of tenmark-wash challenges.

At all times the wax pencil provided a precise and legible mark on thedry surface which was easily rinsed off with water. There was nonoticeable change in the ability of the wax pencil to mark the surfaceor in the ability of the water to wash away the mark over the course ofthe test.

The durability of these treatments was further demonstrated by showingthe resistance of the treated glass surfaces to fogging. The surfaceswere subjected to ten fogging cycles. Each cycle consisted of breathingon the treated glass surfaces; observing the presence or absence offogging thereon; and then drying the surfaces by gentle wiping with adry Colitho® plate wipe. No fogging was observed after any of thecycles.

EXAMPLE 23

A glass microscope slide was cleaned and activated as described inExamples 10-21. A thin layer of the organosilanol-sulfonic acidtreatment solution of Example 2 was immediately applied to one half ofthe slide. After conditioning for 15 minutes at 23° C. the slide wasrinsed with tap water and wiped dry with a Colitho® plate wipe. Theresulting hydrophilic layer was thin, durable and optically transparent.A quantitative verification of the lack of optical impairment by thehydrophilic layer was provided by measuring the % transmittance and the% reflectance of the treated and untreated portions of the slide. AGardner Hazemeter using a General Electric RP11 lamp with a Hunter Ygreen filter as a light source was used for the measurements. Thetransparency of the treated and untreated areas of the slide are setforth in Table 2. As can be seen from the data, the hydrophilictreatment caused no adverse effect upon the transparency of the glassslide.

                  TABLE 2                                                         ______________________________________                                                                    UNTREATED                                         AIR         TREATED GLASS   GLASS                                             ______________________________________                                        % Trans-                                                                      mittance                                                                              100.0   92.0            92.0                                          % Reflect-                                                                    ance     0.0     0.2             0.1                                          ______________________________________                                    

EXAMPLE 24

Example 2 was repeated except that radioactive (³⁵ S) sodium sulfite(available from Amersham/Searle Corporation) was employed in place ofnon-radioactive sodium sulfite. The resultant aqueous treatment solutionof radiolabelled organosilanol-sulfonic acid was applied to separateglass microscope slides which had been cleaned and activated asdescribed in Examples 10-21. The slides were conditioned at 23° C. for15 minutes. They were then subjected to 5 cycles in the Cyclic Weartest, rinsed with deionized water and air dried at 23° C.

The radioactivity of the thin, durable, transparent hydrophilic surfacewas quantitatively determined with a flow-counter gas ionization system(Model 186 from Nuclear-Chicago Corporation). From the data obtained itwas determined that there were an average of 10.3 molecules of theorganosilanol-sulfonic acid compound per square nanometer of surfacearea on the treated portion of the glass slide.

EXAMPLE 25

Two glass surfaces were cleaned and activated as described in Examples10-21. The surfaces were made durably hydrophilic by immediatelyapplying a thin layer of the organosilanol-sulfonic acid treatmentsolution of Example 2. One of the treated surfaces was conditioned for 3hours at 23° C. while the other was conditioned for 15 minutes at 23° C.

The hydrophilicity of the treated surfaces was demonstrated by applyinga section of Scotch® Brand Magic Mending Tape and a section of No. 222autoclave tape (commercially available from Minnesota Mining andManufacturing Company) to each of the treated substrates. Initially,each of the tapes adhered well to the glass. However, when the treatedsurfaces were sprayed with, or immersed, in water the tapes eachexhibited virtually no adherence to the surfaces. There was nonoticeable difference in hydrophilicity based on conditioning time.

Additionally, adhesives such as Duco® Cement (available from E. I.duPont deNemours Company), EC-847 (available from Minnesota Mining andManufacturing Company), and Silastic 732-RTV (available from GeneralElectric Company) were easily removed by simple water rinsing from thetreated surfaces.

EXAMPLE 26

The durable hydrophilicity of the hydrophilic treatment of the inventionwas demonstrated by showing its resistance to repeated exposure tofogging conditions. One half of a bathroom mirror was cleaned andactivated as described in Examples 10-21. This portion of the mirror wasthen immediately dried and treated with the organosilanol-sulfonic acidtreatment solution of Example 2. The treated portion of the mirrorresisted fogging in conditions of high humidity for at least six monthswhile the untreated portion of the mirror repeatedly fogged in suchconditions.

EXAMPLE 27

This Example demonstrates the reversible hydrophilicity of siliceoussubstrates treated in accordance with the present invention. Example 25was repeated on a glass surface and with a conditioning time of 15minutes at 23° C. The hydrophilic surface was then rendered hydrophobicby ion exchange by rinsing it with deionized water and then a 0.1% byweight solution of hexadecyltrimethylammonium chloride in deionizedwater. Then the surface was subsequently rendered hydrophilic by rinsingit with a 0.1% by weight solution of sodium chloride in deionized waterto replace the quaternary ammonium cations with sodium cations. Thenature of the surface can be changed from hydrophilic to hydrophobic tohydrophilic, etc. many times with no noticeable effect on theappropriate (i.e., hydrophilic or hydrophobic) nature thereof.

The hydrophilicity and hydrophobicity of the surface after eachconversion was shown by the Spreading Water Drop test. After the surfacehad been rendered hydrophilic the water drop covered an area of at least18 mm². After the surface had been rendered hydrophobic the water dropcovered an area of less than 3 mm².

EXAMPLES 28-32

Several glass slides were cleaned and activated as described in Examples10-21. One half of each slide was then immediately made durablyhydrophilic by applying a thin layer of one of the aqueous treatmentsolutions according to the present invention. The slides were thentested for wettability and cleanability after exposure to an acceleratedweathering test and an elevated temperature test. Separate slides wereused for each test.

The accelerated weathering test was performed with a "Q-U-V" acceleratedweathering instrument (available from the Q Panel Company). Theinstrument employed an eight hour cycle which consisted of a four hourexposure to ultraviolet light at 60° C. followed by a four hourcondensation period at 50° C. The elevated temperature test wasperformed by placing the treated slides in sealed containers and placingthe containers in ovens at 60° C. and 110° C.

Wettability of the treated and untreated portions of the slides wasdetermined by the Spreading Water Drop Test. Cleanability was determinedby measuring the ease with which a mark made by a wax pencil (Reliance®All Surface Writer, White No. 3366) was removed by simple water rinsing.Failure was deemed to have occurred when either the wettability orcleanability of the treated portion of the slide was approximately equalto that of the untreated portion of the glass slide. The treatmentcompounds used and the results of the tests are set forth in Table 3. Ascan be seen from this data, the hydrophilic treatments of the presentinvention are very durable.

                                      TABLE 3                                     __________________________________________________________________________                                TIME (HRS) TO OBSERVED FAILURE                    EX-                         ACCELERATED                                                                             HEAT EXPOSURE                           AMPLE TREATMENT COMPOSITION WEATHERING                                                                              60° C.                                                                           100° C.                __________________________________________________________________________    28                                                                                   ##STR21##            22        400         24                          29    (HO).sub.3 SiCH.sub.2 CH.sub.2 CH.sub.2 SO.sub.3.sup.                                               81H.sup.+ >2500     >5000                         30    (HO.sub.3)SiCH.sub.2 CH.sub.2 SO.sub.3.sup. - H.sup.+                                               22        400       >5000                         31    (HO).sub.2 Si(CH.sub.2 CH.sub.2 SO.sub.3.sup. - H.sup.+).sub.2                                      22        400       >5000                         32                                                                                   ##STR22##            *         400       >5000                         __________________________________________________________________________     *Not measured                                                            

EXAMPLE 33

A portion of the organosilanolate-sulfonic acid salt treatment solution(3% by weight solids) of Example 1 was titrated with theorganosilanol-sulfonic acid treatment solution (3% by weight solids) ofExample 2 to form a final treatment solution with a pH of 7. Glassslides were cleaned and activated as described in Examples 10-21 andthen immediately these slides were treated with the neutral treatmentsolution of this Example. The slides were conditioned for about 45minutes at 23° C. The resultant treated surfaces were tested for wax andgrease release and fog resistance as described in Example 22. They werefound to be durably antifogging and repeatedly easily cleanable by waterrinsing after being marked with a wax pencil.

Slides cleaned, activated and treated as described in this Example andthen conditioned for two hours or longer at 23° C. also showedhydrophilic properties as shown by the "Spreading Water Drop" Test. Thusa 1.0 μl drop of deionized water placed on a treated horizontal surfacecovered 21.2 mm² while a 1.0 μl drop of water placed on an untreatedhorizontal surface covered less than about 8 mm².

EXAMPLES 34-59

Neutral and basic treatment solutions were prepared by titrating orneutralizing separate portions of treatment solutions prepared accordingto Examples 2 and 3 in water with lithium hydroxide, sodium hydroxide,potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesiumcarbonate, calcium carbonate, barium hydroxide, tetraethyl ammoniumhydroxide, N-benzyltrimethylammonium hydroxide, tetramethyl guanidineand 3[2-ethoxy(2-ethoxyethoxy)] propylamine. The solutions were appliedto a portion of separate glass slides which had been cleaned andactivated as described in Examples 10-21 to provide durably hydrophilicsurfaces thereon. The hydrophilicity of the treated surfaces wasdemonstrated by their wax release and antifogging characteristics. Waxrelease was measured by marking the surface with a wax pencil (Reliance®All Surface Writer, White No. 3366) and then rinsing the mark off with astream of water from a wash bottle. The resultant wax release was ratedon a scale of 0 to 5 with 0 indicating no significant release and 5indicating complete release.

Antifogging was measured by breathing upon the treated surface andobserving the ability of fog to form thereon. Antifogging was measuredas "poor", "fair", "good", or "excellent". "Poor" indicates that one candetect very little difference in antifogging characteristics between thetreated and untreated portions of the slide. "Fair" indicates that onecan detect some minor areas of fogging on the treated portion of theslide. "Good" indicates that one can observe no fogging on the treatedportion of the slide. "Excellent" indicates that one can observe nofogging on the treated portion and that Newton's rings may be seen whenthe moisture is drying after said treated portion has been breathedupon. The results of the tests are given in Table 4.

                  TABLE 4                                                         ______________________________________                                        TREATMENT                                                                     SOLUTION                   HYDRO-                                             REF-                       PHILICITY                                               ER-                   CON-    WAX    ANTI-                                    ENCE    CA-           DITION  RE-    FOG-                                EX.  EX.     TION     pH   TIME    LEASE  GING                                ______________________________________                                        34   Ex. 2   Li.sup.+ 12.9 3 Days  5      Excellent                           35   Ex. 2   Rb.sup.+ 12.9 3 Days  5      Excellent                           36   Ex. 2   K.sup.+  12.9 3 Days  5      Excellent                           37   Ex. 2   Et.sub.4 N.sup.+                                                                       12.9 3 Days  5      Good                                38   Ex. 2   TMG.sup.+                                                                              12.7 3 Days  4      Fair                                39   Ex. 2   Cs.sup.+ 7.0  2 Hours 5      Excellent                           40   Ex. 2   K.sup.+  7.0  2 Hours 5      Excellent                           41   Ex. 2   Rb.sup.+ 7.0  2 Hours 5      Excellent                           42   Ex. 2   Et.sub.4 N.sup.+                                                                       7.0  2 Hours 4      Fair                                43   Ex. 2   TMG.sup.+                                                                              7.0  16 Hours                                                                              4      Poor                                44   Ex. 2   Li.sup.+ 7.0  2 Hours 5      Excellent                           45   Ex. 2   Mg.sup.+2                                                                              7.6  16 Hours                                                                              5      Excellent                           46   Ex. 2*  Ca.sup.+2                                                                              6.8  16 Hours                                                                              5      Fair                                47   Ex. 2*  Ba.sup.+2                                                                              6.9  3 Hours 4      Poor                                48   Ex. 2   NBTM.sup.+                                                                             12.5 3 Days  4      Fair                                49   Ex. 2   ETOP.sup.+                                                                             10.2 3 Days  4      Poor                                50   Ex. 3   RB.sup.+ 12.7 3 Days  5      Excellent                           51   Ex. 3   Li.sup.+ 11.9 3 Days  5      Excellent                           52   Ex. 3   Cs.sup.+ 12.9 3 Days  5      Excellent                           53   Ex. 3   TMG.sup.+                                                                              12.4 3 Days  5      Fair                                54   Ex. 3   Rb.sup.+ 7.0  2 Hours 5      Excellent                           55   Ex. 3   Li.sup.+ 7.0  2 Hours 5      Excellent                           56   Ex. 3   Cs.sup.+ 7.0  2 Hours 4      Excellent                           57   Ex. 3   TMG.sup.+                                                                              7.0  2 Hours 4      Poor                                58   Ex. 3   Mg.sup.+2                                                                              7.8  16 Hours                                                                              5      Excellent                           59   Ex. 3   Ca.sup.+2                                                                              6.8  16 Hours                                                                              5      Fair                                ______________________________________                                         Et.sub.4 N.sup.+  = Tetraethylammonium                                        TMG.sup.+  = Tetramethylguanidinium                                           NBTM.sup.+  = N-benzyltrimethylammonium                                       ETOP.sup.+  = 3 [-2ethoxy(2-ethoxyethoxy)]propylammomium                      *No surfactant used in treatment solution                                

EXAMPLES 60-64

One-part cleaner-treatment compositions were prepared which comprised 2%by weight of the organosilanol-sulfonic acid of Example 2, 10% by weightof abrasive material, 1% by weight of "Keltrol" thickener (a xanthan gumavailable from Kelco Corporation) and 87% by weight of diluent (82%water and 5% isopropyl alcohol).

About 0.5 g of each composition was applied to a separate piece ofsingle strength window glass (7.6 centimeter by 7.6 centimeter) with apad of cheesecloth using light pressure and a circular polishing motionfor about 30 seconds. This procedure cleaned, activated and treated theglass. The test panels were then buffed dry with a piece of clean, drycheesecloth and conditioned for about 20 minutes at about 23° C. andthen were tested for the durability of the hydrophilic treatment. Ablank test panel (i.e., one having been cleaned but not madehydrophilic) was used as a control. The control panel was cleaned with awater slurry of "Imsil" A-25 amorphous silica (from Illinois MineralCompany) and rinsed with deionized water. Durability of the hydrophilictreatments was shown by the Dye Exchange Test and the Cyclic Wear Test.The absorbance of the rinse solution was determined both initially andafter the treated surface had been subjected to the Cyclic Wear Test.The abrasive materials used in the treatment compositions and theresults of the Test are set forth in Table 5.

                                      TABLE 5                                     __________________________________________________________________________                 ABSORBANCE OF EXCHANGED DYE AFTER CHALLENGES                           ABRASIVE    10    25    50    100   250   500                           EXAMPLE                                                                             MATERIAL                                                                             INITIAL                                                                            CYCLES                                                                              CYCLES                                                                              CYCLES                                                                              CYCLES                                                                              CYCLES                                                                              CYCLES                        __________________________________________________________________________    60    I      .75  .54   .50   .49   .42   .48   .47                           61    II     .82  .55   .51   .45   .43   .42   .43                           62    III    .82  .59   .56   .55   .52   .51   .44                           63    IV     1.03 .64   .63   .51   .49   .48   .46                           64    Control                                                                              .36  .36   .42   .44   .42   .36   .36                           __________________________________________________________________________     I. Imsil A10 amorphous silica (99% by weight less than 10 μm in size,      available from Illinois Minerals                                              II. Insil A15 amorphous silica (99% by weight less than 15 μm in size,     available from Illinois Minerals                                              III. Imsil A25 amorphous silica (99.9% by weight pass through a 400 mesh      screen, available from Illinois Minerals                                      IV. α-Quartz Imsil extracted from Ajax®Brand household cleanser                                                                              

As can be seen from this data, a significant amount of the hydrophiliclayer is present on the treated surfaces even after 500 cycles in theCyclic Wear Test. This demonstrates the durability of the hydrophiliclayer.

A Reliance® All-Surface Writer, White No. 3366 was used to make a waxmark on each of the glass panels after 500 abrasion cycles. The mark waseasily removed from the treated panels with a stream of water from awash bottle and gentle rubbing. However, the control panel requiredrinsing and vigorous rubbing in order to remove the mark.

EXAMPLES 65-67

Separate sections of single strength window glass (7.6 cm by 7.6 cm)were rendered hydrophilic. The section employed in Example 65 wascleaned and activated as described in Examples 10-21 after which theorganosilanol-sulfonic acid treatment solution of Example 2 was appliedthereto. The sections employed in Examples 66-67 (duplicate examples)were cleaned, activated and made hydrophilic by a one-partcleaner-treatment composition which comprised 2% by weight of theorganosilanol-sulfonic acid of Example 2, 10% by weight of Imsil A-10abrasive material, 4% by weight of "Veegum HV" thickener (a magnesiumaluminum silicate available from R. T. Vanderbilt Company) and 84% byweight of diluent (74% water and 10% ethylalcohol).

The treated slides were conditioned at 23° C. for 15 minutes and thensubjected to the Dye Exchange Test and Spreading Water Drop Test bothinitially (i.e., before normalization of the surface) and finally afternormalization of the treated surface with the chromic-sulfuric acidtreatment described previously. The results of the tests are given inTable 6.

                  TABLE 6                                                         ______________________________________                                                               SPREADING                                              ABSORBANCE             WATER DROP                                                                      RATIO   IN-                                          EX-    IN-               INITIAL/                                                                              ITIAL  FINAL*                                AMPLE  ITIAL    FINAL*   FINAL*  (mm.sup.2)                                                                           (mm.sup.2)                            ______________________________________                                        65     0.64     0.23     2.78    18.1   6.6                                   66     0.48     0.20     2.40    13.2   4.9                                   67     0.38     0.22     1.73    13.2   4.9                                   ______________________________________                                         *FINAL = Normalized                                                      

EXAMPLES 68-70

Three compositions were prepared. One composition (Example 68) was aone-part cleaner-treatment composition according to the invention. Theother two compositions (Examples 69-70) were surfactant compositions(i.e., they contained no sulfonato-silanol). Each composition wasapplied to separate test panels of single strength window glass with acheesecloth pad using light pressure and a circular polishing patternfor about 30 seconds. The panels were then buffed dry with a clean, drypad of cheesecloth and conditioned for 20 minutes at about 23° C. Thecompositions (in parts by weight) employed in these Examples are setforth in Table 7.

                  TABLE 7                                                         ______________________________________                                        FORMULATION       68       69       70                                        ______________________________________                                        Organosilanol-sulfonic acid                                                   of Example 2      2        --       --                                        Imsil A-25        10       10       --                                        "Keltrol"         1        1        --                                        2-propanol        5        5        --                                        Water (Deionized) 82       82       98                                        "Siponate DS-10" (Sodium                                                      dodecylbenzenesulfonate,                                                      available from Alcolac,                                                       Incorporated)     --       2        2                                         ______________________________________                                    

After conditioning, the test panels were subject to a 500 Cycle CyclicWear Test. A Reliance® All-Surface Writer, White No. 3366 was then usedto make a wax mark on each of the test panels. The mark was easilyremoved from the panel of Example 68 with a stream of water from a washbottle and gentle rubbing. However, the panels of Examples 69 and 70required rinsing and vigorous rubbing in order to remove the marks.

EXAMPLES 71-73

One part cleaner-treatment compositions according to the invention wereprepared and applied to separate test panels of single strength windowglass. The panels were then buffed and conditioned as described inExamples 68-70. Durability of the hydrophilic treatments wasdemonstrated by the Spreading Water Drop Test. An initial determination(i.e., before challenge) and a determination after various numbers ofchallenges was made. The challenges were performed in accordance withthe Cyclic Wear Test. The formulations (in parts by weight) employed andthe results obtained from the "Spreading Water Drop" Test are set forthin Table 8.

                  TABLE 8                                                         ______________________________________                                        FORMULATION       71       72       73                                        ______________________________________                                        Organosilanol-sulfonic acid                                                   of Example 2      2        2        2                                         Imsil A-25        10       10       10                                        Keltrol           1        1        1                                         Siponate DS-10    0.2      2        5                                         2-propanol        5        5        5                                         Deionized Water   81.8     81       77                                        Spreading Water Drop*                                                         (Area in mm.sup.2)                                                            Initial (0 cycles)                                                                              13.4     14.7     20.6                                      10 Cycles         13.4     16.1     16.1                                      25 Cycles         13.4     18.3     16.1                                      100 Cycles        13.4     15.4     14.0                                      500 Cycles        10.3     13.4     14.7                                      ______________________________________                                         *A cleaned but untreated glass panel had a "Spreading Water Drop" Test of     about 8 mm.sup.2.                                                        

A Reliance® All-Surface Writer, White No. 3366 was used to make a waxmark on each of the glass panels after 500 cycles. The mark was easilyremoved from the panels with a stream of water from a wash bottle.

EXAMPLE 74

A silicon monoxide primer coating was deposited on a polyester (i.e.,poly(ethyleneterephthalate) film. The film was coated in a conventionalvapor coating bell jar using a vacuum of 10⁻³ to 10⁻⁴ Torr. A liquidnitrogen trap was interposed between the vacuum pump and the bell jar tosubstantially eliminate back diffusion of organic vapors into the belljar. Chunks of silicon monoxide (i.e., --SiO_(x) -- where x is ≧1<2,available commercially as Kemet® from Union Carbide Corporation) wereplaced in a crucible and heated to 1400°-1700° C. in the bell jar undervacuum (below 10⁻³ Torr) so that the vaporized silicon monoxidecondensed on the surface of the polyester at a rate of 0.5 to 2.5nanometers per second (nm/sec). The thickness of the coating wassubsequently estimated to be 50 nm thick by use of an Inficon CrystalDeposition Detector. Two months later a clean pad (a Colitho® platewipe) was used to apply a thin, visibly damp film of a treatmentsolution containing 3% by weight of the organosilanosulfonic acid ofExample 2, 0.3% by weight sodium dodecylbenzenesulfonate and 96.7% byweight waterethanol (4:1 by volume) to the silicon monoxide coatedpolyester sheet (7.62 cm×7.62 cm). The hydrophilic film was conditionedat 23° C. for three hours. The surface was subsequently scrubbed threestrokes with a wet Colitho® plate wipe followed by drying with a dryColitho® plate wipe. The Spreading Water Drop area was determined to be18 mm². A dye absorbance of 1.39 was measured by the Cationic DyeExchange Test on a 7.6 cm by 7.6 cm section. The dye absorbance of anuntreated silicon monoxide vapor coated polyester sheet of the same sizewas 0.14. The treated sheet released wax pencil markings from aReliance® All-Surface Writer, White No. 3366) and skin oil with simplewater rinsing. Additionally, the treated sheet could be renderedreversibly hydrophilic and hydrophobic as described in Example 27.

EXAMPLES 75-94

Additional substrates were primed with silicon monoxide and rendereddurably hydrophilic as described in Example 74 except that the timeelapsed between vapor coating and hydrophilic treatment varied from 5minutes to two days, thereby indicating that the silicon monoxide coatedsubstrates remained sufficiently activated over an extended period oftime. The estimated thickness of the silicon monoxide layer and theresults of the Spreading Water Drop Test are set forth in Table 9.

                  TABLE 9                                                         ______________________________________                                                                          Spreading                                                           --SiO.sub.x --) (                                                                       Water Drop                                                          Thickness Test Area                                   EXAMPLE  POLYMER        (nm)      (mm.sup.2)                                  ______________________________________                                        75       Plexiglas®.sup.1                                                                         25        18.1                                        76       Polycast®.sup.2                                                                          25        18.1                                        77       Polycarbonate.sup.3                                                                          25        18.1                                        78       Polyvinylchloride                                                                            25        18.1                                        79       Polyvinylfluoride                                                                            25        15.2                                        80       Polyvinylidenefluoride                                                                       15        15.2                                        81       Teflon.sup.4   15        15.2                                        82       Kapton®.sup.5                                                                            25        18.1                                        83       Phenol-formaldehyde                                                                          25        12.3                                                 resin                                                                84       Polyethylene   15        13.2                                        85       Mica           15        15.2 to 18.1                                86       Polycarbonate.sup. 3                                                                         5.8       12.3                                        87       Acrylonitrile/                                                                butadiene/styrene                                                             copolymer      6.5       13.2                                        88       Formica®.sup.6                                                                           6.5       15.2                                        89       Aluminum Foil  6.5       15.2                                        90       Nylon          6.5       9.1 to 13.2                                 91       Polystyrene    12        12.3                                        92       Cellulose Acetate                                                             Butyrate       12        12.3                                        93       Polypropylene  12        15.2                                        94       Scotchlite®.sup.7                                                                        6.5       12.3                                                 No. 3270                                                             ______________________________________                                         .sup.1 Poly-methylmethacrylate commerically available from Rohm & Haas        Company.                                                                      .sup.2 Poly-methylmethacrylate commerically available from Polycast           Technology Corporation.                                                       .sup.3 Polymethylmethacrylate commerically available from Rowland Company     .sup.4 Polytetrafluoroethylene, commerically available from E. I. duPont      de Nemours and Company.                                                        .sup.5 Polyimide commerically available from E. I. du Pont de Nemours an     Company.                                                                      .sup.6 Melamine resin commericallly available from Formica Corporation.       .sup.7 Reflective sheeting commerically avaliable from Minnesota Mining       and Manufacturing Company.                                               

The Spreading Water Drop test demonstrates that the treated surfaceswere hydrophilic. This hydrophilicity was further demonstrated by makinga wax pencil mark on each of the surfaces with a Reliance® All-SurfaceWriter, White No. 3366. The wax mark was readily removed from each ofthe surfaces by simply rinsing the surfaces with a stream of water froma wash bottle.

EXAMPLE 95-98

Various siliceous surfaces were cleaned, activated, treated, andconditioned using the composition and procedures of Example 23. Thesubstrates treated and the results obtained are given in Table 10.

                  TABLE 10                                                        ______________________________________                                        Example Surface      Results                                                  ______________________________________                                        95      Glass Slide  Antifogging and easily released                                               grease for over one year                                                      with gentle water washing.                               96      Indoor Window                                                                              Easily cleaned after one                                         Glass        year by wiping with wet                                                       towel despite not having                                                      been otherwise cleaned.                                                       An uncleaned section of                                                       glass required considerable                                                   effort in order to clean.                                97      Eyeglasses   Provided antifogging prop-                                                    erties for two to four weeks                                                  during winter months.                                    98      Exterior Auto                                                                              Improved visibility during                                       Windshield   rainfall on treated portion.                                                  Improved cleanability by                                                      low friction action of wind-                                                  shield wipers.                                           ______________________________________                                    

EXAMPLE 99

A portion of a 7.5 cm×7.5 cm panel of single-strength window glass wascleaned, activated, treated and conditioned using the composition andprocedures described in Example 23. Both the treated portion and theuntreated portion of the glass panel was deliberately contaminated inseparate areas by the following synthetic and natural greases andfluids:

    ______________________________________                                        Silicone Stopcock Grease                                                                         (Dow Corning Co.)                                          Apiezon T Vacuum Grease                                                                          (Associated Electrical                                                        Industries, Ltd.)                                          Santovac 5 (a polyphenyl                                                                         (Monsanto Corp.)                                           ether fluid)                                                                  FS Fluorosilsicone Grease                                                                        (Dow Corning Co.) -Aroclor 1242 (a chlorinated (Monsant                       o Corp.)                                                   byphenyl fluid)                                                               Fomblin-SH Fluorinated Fluid                                                                     (available from Penisular                                                     Chemical Co.)                                              Kel-F No. 90 Grease (a                                                                           (Minnesota Mining and                                      chlorotrifluoroethylene polymer)                                                                 Manufacturing Company)                                     Bis(2-ethyl hexyl)adipate                                                     (a diffusion pump fluid)                                                      Linseed oil, peanut oil, olive oil, cottonseed oil,                           and neatsfoot oil.                                                            ______________________________________                                    

Without exception, these substances were quickly released from thetreated glass surface upon gentle rinsing with a thin stream of tepidtap water. There was no trace of contamination upon drying the rinsedand treated area. However, the untreated portion remained grosslycontaminated, and in most cases, the areas of contamination of saiduntreated portion increased upon similar rinsing.

EXAMPLE 100

A 7.5 cm by 7.5 cm panel of single-strength window glass was cleaned,activated, treated and conditioned using the composition and proceduredescribed in Example 23. A portion of the treated surface was rinsedfirst with tap water and then ion exchanged by rinsing with about 1 ml.of a 1% by weight aqueous solution of the fluorinated quaternaryammonium salt, C--C₈ F₁₇ SO₂ NHCH₂ CH₂ CH₂ N(CH₃)₃ ⁺ Cl⁻. It was thenrinsed with deionized water. The exchanged surface became reversiblyhydrophobic and additionally, exhibited reversible oleophobic behavior.Thus, when S.A.E. No. 10 lubricating oil was applied dropwise to theexchanged and unexchanged surface, it remained in non-spreading drops onthe dried exchanged portion surface but slowly spread on the unexchangedportion. The oleophobic exchanged surface was connected directly to anoleophibic but hydrophobic surface by rinsing with 1% aqueoushexadecyltrimethylammonium chloride followed by deionized water rinsing.

EXAMPLE 101

A section of single-strength window glass was selectively cleaned,activated and rendered hydrophibic with the composition and according tothe procedures of Example 23 so as to leave a portion of the glassuntreated. The untreated section was surrounded by the treated section.

The treated portion of the glass was then selectively renderedoleophobic using the quaternary salt and method described in Example 100so as to leave a portion thereof non-oleophobic. THe glass was thenrinsed with deionized water leaving both the untreated area and thetreated hydrophibic area (i.e., nonoleophobic area) surrounded by theoleophobic area.

S.A.E. No. 10 lubricating oil was dropped onto the untreated area andonto the treated hydrophilic area. The oil remained in said areas eventhough the panel was tilted and shaken. Additionally, the oleophobicarea resisted the spread of drops of acetone which were placed thereonwhile the treated hydrophilic area permitted the spread of drops ofacetone placed thereon.

What is claimed is:
 1. An aqueous solution comprising asulfonato-organosilanol compound having at least one sulfonato-organicsubstituent, wherein the weight percentage of oxygen in said compound isat least about 30%, and the weight percentage of silicon in saidcompound is not greater than about 15%, said percentages being takenwith reference to the water-free acid form of said compound.
 2. Asolution in accordance with claim 1 wherein said sulfonato-organosilanolcompound has the formula ##STR23## wherein Q is selected from hydroxyl,alkyl groups containing from 1 to about 4 carbon atoms and alkoxy groupscontaining from 1 to about 4 carbon atoms;M is selected from hydrogen,alkali metals and organic cations of strong organic bases having anumber average molecular weight of less than about 150 and a pK_(a) ofgreater than about 11; X is an organic linking group; Y is selected fromhydrogen, alkaline earth metals, cations of protonated weak bases havingan average molecular weight of less than about 200 and a pK_(a) of lessthan about 11, alkali metals and organic cations of strong organic baseshaving an average molecular weight of less than about 150 and a pK_(a)of greater than about 11, provided that M is hydrogen when Y is selectedfrom hydrogen, alkaline earth metals and organic cations of saidprotonated weak base; r is equal to the valence of Y; and n is 1 or 2.3. A solution in accordance with claim 2 wherein X is selected fromalkylene groups, cycloalkylene groups, alkyl-substituted cycloalkylenegroups, hydroxy-substituted alkylene groups, hydroxy-substitutedmono-oxa alkylene groups, divalent hydrocarbon groups having mono-oxabackbone substitution, divalent hydrocarbon groups having mono-thiabackbone substitution, divalent hydrocarbon groups having monooxo-thiabackbone substitution, divalent hydrocarbon groups having dioxo-thiabackbone substitution, arylene groups, arylalkylene groups, alkylarylenegroups and substitutied alkylarylene groups.
 4. A solution in accordancewith claim 3 wherein X is selected from alkylene groups,hydroxy-substituted alkylene groups and hydroxy-substituted mono-oxaalkylene groups.
 5. A solution in accordance with claim 2 wherein saidsulfonato-organosilanol compound comprises an organosilanol-sulfonicacid of the formula ##STR24##
 6. A solution in accordance with claim 5having a pH of less than about
 5. 7. A solution in accordance with claim5 wherein said organosilanol-sulfonic acid has the formula (HO)₃ SiXCH₂SO₃ ⁻ H⁺.
 8. A solution in accordance with claim 7, wherein X is--(CH₂)_(m) --, where m is an integer of from 1 to about
 8. 9. Asolution in accordance with claim 8 wherein m is
 1. 10. A solution inaccordance with claim 8 wherein m is
 2. 11. A solution in accordancewith claim 7 wherein X is ##STR25##
 12. A solution in accordance withclaim 5 wherein said organosilanol-sulfonic acid has the formula##STR26##
 13. A solution in accordance with claim 12 wherein X is --CH₂--.
 14. A solution in accordance with claim 5 wherein saidorganosilanol-sulfonic acid has the formula ##STR27## wherein Q is analkyl group containing from 1 to about 4 carbon atoms.
 15. A solution inaccordance with claim 2 wherein said sulfonato-organosilanol compoundcomprises an organosilanolate-sulfonic acid salt wherein M and Y areeach selected from alkali metals and organic cations of strong organicbases having an average molecular weight of less than about 150 and apK_(a) of greater than about
 11. 16. A solution in accordance with claim15 having a pH greater than about
 9. 17. A solution in accordance withclaim 15 wherein Q is selected from hydroxyl, alkyl groups containingfrom 1 to about 4 carbon atoms and alkoxy groups containing from 1 toabout 4 carbon atoms, provided that at least one of said Q groups ishydroxyl.
 18. A solution in accordance with claim 15, wherein n is 2 andr is
 1. 19. A solution in accordance with claim 2 wherein saidsulfonato-organosilanol compound comprises an organosilanol-sulfonicacid salt wherein M is hydrogen; Q is selected from hydroxyl and alkylgroups of from 1 to about 4 carbon atoms and Y is selected from alkalineearth metals, cations of protonated weak bases having an averagemolecular weight of less than about 200 and a pKa of less than about 11,alkali metals and cations of strong organic bases having an averagemolecular weight of less than about 150 and a pKa of greater than about11.
 20. A solution in accordance with claim 19 having a pH in the rangeof about 5 to
 9. 21. A solution in accordance with claim 19, wherein Qis hydroxyl.
 22. A solution in accordance with claim 21, wherein n is 2and r is
 1. 23. A solution in accordance with claim 21 wherein n and rare each
 1. 24. A solution in accordance with claim 1 further comprisinga surfactant.
 25. An organosilanol sulfonic acid having the formula##STR28## wherein Q is selected from hydroxyl, alkyl groups containingfrom 1 to about 4 carbon atoms and alkoxy groups containing from 1 toabout 4 carbon atoms; X is an organic linking group; and n is 1 or 2;wherein the weight percentage of oxygen in said compound is at leastabout 30%, and the weight percentage of silicon in said compound is notgreater than about 15%; said percentages being taken with respect to thewater-free acid form of said compound.
 26. An organosilanol-sulfonicacid in accordance with claim 25 wherein X is selected from alkylenegroups, cycloalkylene groups, alkyl-substituted cycloalkylene groups,hydroxy-substituted alkylene groups, hydroxy-substituted mono-oxaalkylene groups, divalent hydrocarbon groups having mono-oxa backbonesubstitution, divalent hydrocarbon groups having mono-thia backbonesubstitution, divalent hydrocarbon groups having mono-oxa thia backbonesubstitution, divalent hydrocarbon groups having dioxo-thia backbonesubstitution, arylene groups, arylalkylene groups, alkylarylene groups,and substituted alkylarylene groups.
 27. An organosilanol-sulfonic acidin accordance with claim 26 wherein X is selected from alkylene groups,hydroxy-substituted alkylene groups and hydroxy-substituted mono-oxaalkylene groups.
 28. An organosilanol-sulfonic acid in accordance withclaim 25 having the formula (HO)₃ Si--X--CH₂ SO₃ ⁻ H⁺.
 29. Anorganosilanol sulfonic acid in accordance with claim 28 wherein X is--CH₂ --_(m), where m is an integer of from 1 to about
 8. 30. Anorganosilanol sulfonic acid in accordance with claim 29 wherein m is 1.31. An organosilanol sulfonic acid in accordance with claim 29 wherein mis
 2. 32. An organosilanol sulfonic acid in accordance with claim 27wherein X is ##STR29##
 33. An organosilanol sulfonic acid in accordancewith claim 25 having the formula ##STR30##
 34. An organosilanol-sulfonicacid in accordance with claim 33 wherein X is --CH₂ --.
 35. Anorganosilanolate-sulfonic acid salt having the formula ##STR31## whereinQ is selected from hydroxyl, alkyl groups containing from 1 to about 4carbon atoms and alkoxy groups containing from 1 to about 4 carbonatoms; Z is selected from alkali metals and cations of strong organicbases having an average molecular weight of less than about 150 and apK_(a) of greater than about 11; r is equal to the valence of Z; and nis an integer of 1 or 2;wherein the weight percentage of oxygen in saidcompound is at least about 30%; and the weight percentage of silicon insaid compound is not greater than about 15%, said percentages beingtaken with respect to the water-free acid form of said compound.
 36. Anorganosilanolate-sulfonic acid salt in accordance with claim 35 whereinZ is selected from sodium, potassium, (CH₃)₄ N⁺, and (CH₃ CH₂)₄ N⁺. 37.An organosilanolate-sulfonic acid salt in accordance with claim 35wherein n is 2 and r is
 1. 38. An organosilanolate-sulfonic acid salt inaccordance with claim 35, wherein n is 1 and r is 1.